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By Robert E. Cuthbertson

It is the purpose of this paper to describe in detail the laboratory development and mill application of an unusual combination of flotation reagents employed in the concentrator of the Climax Molybdenum Co., on the Continental Divide, near Leadville, Lake County, Colorado. This development originated in an ore-dressing research laboratory maintained by Climax at the experimental plant of the Colorado School of Mines, which is staffed by men directly employed by the Climax Molybdenum Co. Mill-scale testing of laboratory developments was supervised by a representative from the testing laboratory, working in close cooperation with the operating staff at the mill. General milling practice at Climax is ably described in a paper by E. J. Duggan,1 mill superintendent. Other aspects of the Climax project have been described in papers by W. J. Coulter,2 by Butler, Vanderwilt and Henderson,= by Allen Kissock,4 and by Leo H. Glanville.5 Consequently, this paper will be corfined to the metallurgical aspects of recent reagent developments, avoiding, as much as possible, repetition of material covered in these earlier publications. Brief History of Reagent Practice at Climax Prior to the year 1937, the only reagents employed at Climax for froth production and collecting action in the flotation of molybdenite were steam-distilled or destructively distilled pine oils. The only exceptions to this practice were brief periods of mill testing, when reagents of various types were tried on an experimental basis. None of these experimental runs was sufficiently encouraging to justify its continuation as regular practice. Sodium cyanide has been employed since the very early days of milling at Climax as an inhibiting agent for control of pyrite and chalcopyrite. Alkaline reagents such as lime or soda ash have been used in recent years to minimize the detrimental effect of iron salts on flotation of molybdenite. The presence of these harmful salts is attributed to the decomposition of fine metallics abraded from liners and balls in the first stage of regrinding rougher concentrate. Flint pebbles are used in subsequent regrinding, since alkaline reagents are not entirely adequate to offset the inhibiting effect of iron salts as the grind becomes progressively finer and the grade of concentrate progressively higher. Climax metallurgists were familiar at an early date with the use of petroleum products such as kerosene and gas oil as promoters of flotation of molybdenite. Charles C. Oliver6 discussed the use of pine oil and kerosene as early as 19-20, in connection with the milling practice at Dominion Molybdenite Co., Quebec. Nevertheless, the early attempts to apply this knowledge in the Climax concentrator were complete failures. In the light of recent experience, it may seem strange that the early mill tests with petroleum

Jan 1, 1947

By Cyril Stanley Smith, Earl W. Palmer

STRIP of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner. Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal. The effect is known as "earing" and the protuberances are called "ears." Other terms frequently heard are "tips," "scallops," and "corners." It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip. 'Numerous papers dealing with various aspects of the earing effect have appeared in the literature, those listed in the references1 being especially interesting and valuable. An investigation of the factors influencing earing of brass cups has been in progress in the laboratories of the American Brass Co. for several years, and it was thought desirable to make some of the results generally available in summarized form. The present paper discusses many factors that do and do not contribute to ear formation. In addition, a section is devoted to methods of minimizing the earing tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced. In the space available, it is impossible to quote detailed experimental procedures and numerical results. However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill. MECHANISM OF EAR FORMATION It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions. The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup. A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip. The two-ear form that sometimes appears is also traceable to gauge variations. However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself.

Jan 1, 1942

By Earl W. Palmer, Cyril Stanley Smith

StKip of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner. Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal. The effect is known as "earing" and the protuberances are called "ears." Other terms frequently heard are "tips," "scallops," and "corners." It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip. Numerous papers dealing with various aspects of the earing effect have appeared in the literature, those listed in the references1 being especially interesting and valuable. An investigation of the factors influencing earing of brass cups has been in progress in the laboratories of the American Brass Co. for several years, and it was thought desirable to make some of the results generally available in summarized form. The present paper discusses many factors that do and do not contribute to ear formation. In addition, a section is devoted to methods of minimizing the earing tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced. In the space available, it is impossible to quote detailed experimental procedures and numerical results. However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill. Mechanism of Ear Formation It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions. The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup. A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip. The two-ear form that sometimes appears is also traceable to gauge variations. However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself.

Jan 1, 1942

By Cyril Stanley Smith, Earl W. Palmer

StKip of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner. Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal. The effect is known as "earing" and the protuberances are called "ears." Other terms frequently heard are "tips," "scallops," and "corners." It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip. Numerous papers dealing with various aspects of the earing effect have appeared in the literature, those listed in the references1 being especially interesting and valuable. An investigation of the factors influencing earing of brass cups has been in progress in the laboratories of the American Brass Co. for several years, and it was thought desirable to make some of the results generally available in summarized form. The present paper discusses many factors that do and do not contribute to ear formation. In addition, a section is devoted to methods of minimizing the earing tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced. In the space available, it is impossible to quote detailed experimental procedures and numerical results. However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill. Mechanism of Ear Formation It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions. The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup. A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip. The two-ear form that sometimes appears is also traceable to gauge variations. However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself.

Jan 1, 1942

E. P. Pfleider, University of Minnesota I would like to ask Bob Merrill whether he considers that horizontal concave curvature of a slope has any stabilizing effect, such as Jenike 1 suggested several years ago. R. H. Merrill, U. S. Bureau of Mines, Denver Federal Center The stabilizing effect is due to the restraint offered to radial movement by the curvature. We found in laboratory tests that if we constrained the rock with the same stresses as those measured in the pit then it would sustain a maximum stress about two or four times greater than when the same rock type was unconstrained. We are therefore definitely of the opinion that a constrained situation in a slope is favorable towards stability. G. A. Leonards, Purdue University I was interested in Mr. Lane's observations concerning the correspondence between rate of slide movement with rise of reservoir. Perhaps the most interesting feature is that the rate of movement at the time the rock slope failed was less than the rate at an earlier time when it did not fail. This is difficult to explain from current slope stability theory. K. S. Lane, U. S. Army Corps of Engineers I believe that reduced rate of movement is the result of the progressive type of failure, such as described by Patton and Deere. which occurs along the sliding surfaces. It is difficult to analytically define the progressive failure condition for inclusion in slope stability conditions, but its existence should be recognized in design. We should also realize that many apparently stable slopes undoubtedly contain overstressed regions. To design a slope with no overstressed region would be uneconomical and conservative. D. H. Deere I would pose the question-"What is the meaning of a factor of safety of one?" We were involved in the design of a large, irregularly shaped, underground cavity with an unsupported span of several hundreds of feet. Tests on rock specimens indicated a strength of 1300 lb per sq in. The RQD would have been between 90 to 100 percent indicating excellent structural continuity. In-situ stress determinations indicated an approximately hydrostatic state of stress at a level of 1400 lb per sq in. Calculation of stress concentrations at the walls indicated that the stresses there would be about 3000 to 4000 lb per sq in. Admittedly the rock is in a confined condition everywhere except at the very skin of the wall and the rock walls would thus on the average be somewhat stronger. Allowing for the effect of restraint the factor of safety was found to be less than 0.5 over a region several feet into the wall. Construction was started, using rockbolts only to support the walls. Failure around the immediate skin occurred after each

Jan 1, 1967

By Henry N. Doyle

Basic procedures in the mining industry have changed only slightly over the centuries since metals and fossil fuels became an essential part of man's economic and cultural life. Mining techniques of the 20th century bear a close resemblance to those of the ancients: exploration, ore breakage and removal, hoisting, and processing. The great advances, however, have been in equipment and machinery of greater size and speed which allow greater efficiency in each of these operations, with a corresponding reduction in manpower requirements. Yesteryear production was measured in pounds per man-day; today a giant and complex, but highly efficient, continuous mining machine can remove as much as eight tons of material a minute from the coal face. If our energy and metal demands of the future are to be met, and at this time it can be assumed that coal will continue to supply a significant part of the energy demand, other dramatic and spectacular technologic advances must be accomplished. Along with mechanization, however, public policy will require the industry to place greater emphasis on health and safety protection, as has been well demonstrated by recent actions of Congress. Together, fossil fuels and metals formed the basis for the industrial revolution-coal to develop power and metals to transform power into useful energy. Strangely enough, however, the mining industry the world over has lagged behind the continuous social changes brought on by the industrial revolution, such as preventive health and industrial hygiene services, and other programs directed to the well-being of the worker. In some countries this resistance, to change may have led in part to the nationalization of the coal industry. Whether this disinclination to social change in the industry of the United States reflects managerial attitudes, inept labor leadership, government neglect, or economic relationship would be the subject of an interesting study. Doubtless the mores of miners and their resistance to change, as well as their geographic isolation from other industrial groups, may have had a strong influence on these factors. In every major coal mining country the accident rate in the coal industry is substantially higher than other industrial groups, and the cost of pneumoconiosis compensation in some countries is greater than the combined costs for all other occupational diseases from all other industries. The high social cost of occupational accidents and diseases may have been a factor in the closing of the industry in at least two countries. Despite diminishing manpower needs, the industry is faced with critical manpower shortages. Miners once reared their sons to be miners; now it appears that the opposite is true. This factor alone, however, does not explain an acute labor shortage in the industry. Traditionally, the industry drew much of

Jan 1, 1976

By B. M. Larsen, T. E. Brower

IN an earlier paper1 we discussed a simple, rapid method of taking samples of liquid steel and analyzing them for oxygen, which, though possibly not absolutely accurate (as is likewise true of all other methods), certainly yields results that are satisfactorily consistent. Accordingly, samples from hundreds of heats in different shops were analyzed for oxygen, with results sufficient in number to be handled statistically and permit estimation of some general trends. Measurements were made in acid as well as in basic open hearths, throughout the refining period, to learn how stirring, blocking, adding ore or lime or sand, affects the oxygen content of the bath; we also followed the changes brought about by tapping, teeming, and deoxidizing. Some of these results, discussed in an earlier paper.2 bring out the dominant role of the carbon-oxygen reaction in regulating degree of oxidation both of metal and of slag, also the marked variability of concentration of dissolved oxygen [0] in excess of that which would be in equilibrium with carbon and with carbon monoxide at a partial pressure of one atmosphere. As a logical beginning on this complex problem, we take up in the present paper the variability of this excess oxygen, ?[O], when other factors are as constant as they ever are in open-hearth operation; namely, toward the end of the refining period, when the bath may be regarded as in the comparatively steady state it approaches in absence of disturbing factors. This condition was chosen because by that time the significant reactions, except carbon oxidation, between slag and metal have come to substantial equilibrium; this facilitates interpretation of the complex situation and thus permits more definite conclusions to be drawn. This excess concentration of oxygen, ?[0], in the metal is needed, of course, to make the steelmaking process go at a reasonable rate; alternatively it may be regarded as a measure of the virtual pressure increment above one atmosphere, or of the degree of supersaturation, of carbon monoxide in the metal. According to our measurements, the excess concentration ?[O] in liquid steel varies from about 0.009 to 0.035 per cent oxygen by weight. It is quite sensitive to change of conditions, being altered temporarily by operations such as stirring with green poles, additions of ore, lime, or sand; but as the disturbance works itself out, it resumes a level within the intermediate range characteristic of the steady state. The conditions most common in average furnace practice are covered by the following : [ ] as in a reasonably steady state-that is, when it is boiling normally, is at proper temperature with a well-shaped slag, and has been free from disturbing effects during the preceding half hour-?[O] returns from

Jan 1, 1946

By John Chipman, Karl L. Fetters

Tax relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steelmaking processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of laboratory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermodynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component system seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest

Jan 1, 1941

By W. A. Johnson, F. N. Rhines, W. A. Anderson

The rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish- able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1942

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about 15 years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electro-¦ chemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are moditied in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.1-3 In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative arid may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole' These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in pennsylvania, carried out by the pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, ill the published literature. The potential differences across the contacts of sandstone and shale are called ill this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored WeLl In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored With diamond tools. The potentials were first measured with fresh water in the hole. * null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and

Jan 1, 1946

By R. Casting, J. Philibert, and C. Crussard

APPARATUS described in this paper uses the properties of X-radiation, emitted by substances under electron bombardment, as a means of rapid chemical point analysis. The method is based upon the principles of emission X-ray spectrography pioneered by Moseley in 1913. A very finely focused beam of electrons—the electron probe—is projected on the surface of a sample, which has a very large area compared with the beam diameter, at the point where it is desired to know the chemical composition. The minute volume of the sample which is thus irradiated emits a complex X-ray spectrum consisting principally of the characteristic radiations of the elements present in the volume. Measurement of the wavelength and intensity of each component of this spectrum thus affords a simple method of determining the chemical identity and concentration of these elements. The volume of sample which is analyzed at each position of the beam is limited by the diffusion of electrons in the sample. For an accelerating potential of the electron beam of about 30 kv, which is a convenient value for producing the characteristic radiation, this diffusion extends over a diameter of about 1 µ normal to the beam, and about 2 µ in the direction of the beam. Thus a beam of 1 µ in diameter leads to a volume of about 2 µ in diameter being irradiated. The limits of the analyzed region are thus considerably smaller than those obtained by using spark or arc emission spectrometry, which must extend to about 50 µ at right angles to the beam, and those obtained in X-ray fluorescence analysis, where the penetration of the specimen is considerably greater. The apparatus itself consists of three main parts: an electron optical system. an X-ray spectrograph and an optical microscope. The electron opticai system consists of a tungsten cathode emitting the electrow and a pair of magnetic lenses which focus the electron beam on the specimen to be analyzed. The specimen is prepared in the usual way, as in optical micrography. The X-radiation, emitted at the focal spot where the electrons strike the sample, is analyzed with a curved crystal, Geiger-Müller counter, vacuum spectrograph. The light microscope, designed to observe the surface of the sample in the region to be analyzed, is provided with a reflecting objective placed on the axis of the second magnetic lens. Its magnification is X450. The quantitative determination of an element A in the analyzed region is made by measuring the intensity I, of a strong characteristic line of the element, as emitted from the sample, and then the intensity I (A) of this same line as emitted from a

Jan 1, 1958

By Donald B. Hunter

The Ti-Be system up lo 10 wt pct Be with cortlmercialll' pure titanium has been determined using metal-lographic techniques. Beryllium forms the p eutec-toid type of dinqarz with titanium; the eutectoid occurs at 0.5 xt pct Be azd 1500 F, while an eutectic is foritled at 1887°F containing between 5 and 7.5 rt pct Be. The solubility of beryllium in a titanium does not exceed 0.05 zvt pct and the maximum solubility of Beryllim in 0 titanium is 1 wt pet. PREVIOUS work on the Ti-Be phase diagram indicated that additions of beryllium to titanium resulted in a marked lowering of the melting point,''' and it was also observed that the solubility of beryllium in both a and p titanium was retricted.- With the limited data available, McQuillan and McQuillan constructed a partial hypothetical diagram of the Ti-Be system,= assuming that beryllium formed the 0 eutectoid type of system with titanium. Subsequently Bedford published a tentative diagram of the entire Ti-Be system: although he did not investigate alloys containing less than 10 wt pct Be. This diagram included several compounds described by other authorities.'-l3 The following account describes work directed toward determining the form of the titanium-rich portion of the phase diagram up to 10 wt pct Be. MATERIALS AND METHODS Titanium sponge and a master alloy containing 25 wt pct Be were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 250-g compacts which were melted into buttons by arc melting under purified argon on a water-cooled copper hearth. Results of analyses for beryllium are shown in Table I but no determination of other elements was made at this stage. The alloys were hot-rolled at 1650°F to produce 0.1-in.-thick sheet. Alloys containing up to 1.5 pct Be were fabricated without trouble; samples containing 2 pct cracked initially upon hot rolling, but thereafter rolled satisfactorily to sheet. The 5, 7.5, and 10 pct were hot short and could not be rolled. Surface contamination was removed from samples by sandblasting and pickling in a 5 pct HF-35 pct HNOs solution. For metal log raphic examination, heat-treated specimens were mounted transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and electropolished at 20 v using a solution containing 600 ml of methanol, 60 ml of perchloric acid, 360 ml of butyl cellosolve, and 2 ml of Solvent "X". Difficulty was experienced in obtaining good electropolished surfaces with samples containing more than 1 pct Be, the degree of difficulty in-

Jan 1, 1967

By W. A. Anderson, F. N. Rhines, W. A. Johnson

THE rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1941

By W. A. Anderson, F. N. Rhines, W. A. Johnson

The rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish- able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1942

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about 15 years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electro-¦ chemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are moditied in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.1-3 In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative arid may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole' These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in pennsylvania, carried out by the pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, ill the published literature. The potential differences across the contacts of sandstone and shale are called ill this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored WeLl In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored With diamond tools. The potentials were first measured with fresh water in the hole. * null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and

Jan 1, 1946

By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.' During quenching, nearly all of the silver segregates into zones' and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y' and y precipitates.' The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y' plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155' and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7' was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y' precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electrochemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are modified in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.'-a In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative and may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole. These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in Pennsylvania, carried out by the Pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, in the published literature. The potential differences across the contacts of sandstone and shale are called in this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored Well In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored with diamond tools. The potentials were first measured with fresh water in the hole. A null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and crystals surrounding a pure copper elec-

Jan 1, 1944

By George A. Morrison

THE Columbia Chemical Division of the Pittsburgh Plate Glass Co. is at Barberton, Ohio, 35 miles south of Cleveland. For many years large tonnages of limestone have been brought to the Barberton plant from distant points. The stone is here burnt in vertical kilns, the resultant product then hydrated and the hydrated lime used in chemical processing. To eliminate the expense of these shipments, the company decided to investigate a limestone bed known to exist on company property at Barberton, where the stone is used. The bed lay at a depth of more than 2000 ft. and was known locally as the "Deep Lime." Chemical analyses of sludge from churn-drill holes made some years ago proved that the limestone was of sufficient purity to warrant diamond-drill exploration. Four diamond-drill holes were put down at well-spaced intervals, to represent fairly an area of four miles by one mile. Cores logged as to chemical and physical conditions were found to compare closely, and to corroborate the earlier evidence that the limestone was of superior quality for chemical use. A plant of 300 tons per hour was subsequently decided upon. SITE The yard at the chemical plant was already so congested that location of the projected mine within its area could not be considered. Eventually a site was selected 2 miles northwest of the plant, near the main line of the Erie Railroad. Here 412 acres were owned outright by the company and stone rights were obtained on 250 additional acres. This location required a transportation line of nearly 2 miles (8800 ft.), crossing two major highways, and to avoid interruption of deliveries to the plant, overpasses were planned. GEOLOGY The limestone in the immediate vicinity lies about 2200 ft. below the surface. Geologists* identify this stone as Delaware of Devonian age. It is overlain by 18 ft. of unconsolidated (sand and gravel), 100 ft. of water-bearing sandstone, and finally 2080 ft. of shale into which sandstone in thin layers is interbedded. The contact of shale and limestone is abrupt, flat-lying and very pronounced. Berea sandstone, often found at 520 ft., is absent, but Euclid sandstone was encountered, together with a seepage of oil and a small amount of methane gas. The limestone bed itself is 345 ft. thick, and overlies 200 ft. of gypsum. The lower part becomes dolomitic as it approaches the gypsum. A detailed study of the drill cores indicates that the upper 50 ft, are highest in lime and reasonably low in silica. The physical make-up shows several separating cherty layers. These occur at definite horizons and cause distinct partings, which become horizontal planes of

Jan 1, 1943

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electrochemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are modified in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.'-a In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative and may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole. These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in Pennsylvania, carried out by the Pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, in the published literature. The potential differences across the contacts of sandstone and shale are called in this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored Well In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored with diamond tools. The potentials were first measured with fresh water in the hole. A null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and crystals surrounding a pure copper elec-

Jan 1, 1944

By George A. Morrison

The Columbia Chemical Division of the Pittsburgh Plate Glass Co. is at Bar-berton, Ohio, 35 miles south of Cleveland. For many years large tonnages of limestone have been brought to the Barberton plant from distant points. The stone is here burnt in vertical kilns, the resultant product then hydrated and the hydrated lime used in chemical processing. To eliminate the expense of these shipments, the company decided to investigate a limestone bed known to exist on company property at Barberton, where the stone is used. The bed lay at a depth of more than 2000 ft. and was known locally as the "Deep Lime." Chemical analyses of sludge from churn-drill holes made some years ago proved that the limestone was of sufficient purity to warrant diamond-drill exploration. Four diamond-drill holes were put down at well-spaced intervals, to represent fairly an area of four miles by one mile. Cores logged as to chemical and physical conditions were found to compare closely, and to corroborate the earlier evidence that the limestone was of superior quality for chemical use. A plant of 300 tons per hour was subsequently decided upon. SITe The yard at the chemical plant was already so congested that location of the projected mine within its area could not be considered. Eventually a site was selected 2 miles northwest of the plant, near the main line of the Erie Railroad. Here 412 acres were owned outright by the company and stone rights were obtained on 2 50 additional acres. This location required a transportation line of nearly 2 miles (8800 ft.), crossing two major highways, and to avoid interruption of deliveries to the plant, overpasses were planned. Geology The limestone in the immediate vicinity lies about 2200 ft. below the surface. Geologists* identify this stone as Delaware of Devonian age. It is overlain by 18 ft. of unconsolidated (sand and gravel), 100 ft. of water-bearing sandstone, and finally 2080 ft. of shale into which sandstone in thin layers is interbedded. The contact of shale and limestone is abrupt, flat-lying and very pronounced. Berea sandstone, often found at 520 ft., is absent, but Euclid sandstone was encountered, together with a seepage of oil and a small amount of methane gas. The limestone bed itself is 345 ft. thick, and overlies 200 ft. of gypsum. The lower part becomes dolomitic as it approaches the gypsum. A detailed study of the drill cores indicates that the upper 50 ft. are highest in lime and reasonably low in silica. The physical make-up shows several separating cherty layers. These occur at definite horizons and cause distinct partings, which become horizontal planes of

Jan 1, 1946